US7220294B2 - Method for storing hydrogen, hydrogen clathrate compound and production method thereof - Google Patents

Method for storing hydrogen, hydrogen clathrate compound and production method thereof Download PDF

Info

Publication number
US7220294B2
US7220294B2 US10/804,108 US80410804A US7220294B2 US 7220294 B2 US7220294 B2 US 7220294B2 US 80410804 A US80410804 A US 80410804A US 7220294 B2 US7220294 B2 US 7220294B2
Authority
US
United States
Prior art keywords
hydrogen
tetrakis
bis
host compound
hydroxyphenyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime, expires
Application number
US10/804,108
Other languages
English (en)
Other versions
US20040230084A1 (en
Inventor
Minoru Yagi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kurita Water Industries Ltd
Original Assignee
Kurita Water Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kurita Water Industries Ltd filed Critical Kurita Water Industries Ltd
Assigned to KURITA WATER INDUSTRIES LTD. reassignment KURITA WATER INDUSTRIES LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: YAGI, MINORU
Publication of US20040230084A1 publication Critical patent/US20040230084A1/en
Application granted granted Critical
Publication of US7220294B2 publication Critical patent/US7220294B2/en
Adjusted expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
    • C01B3/0015—Organic compounds; Solutions thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/12—Polycyclic non-condensed hydrocarbons
    • C07C15/18—Polycyclic non-condensed hydrocarbons containing at least one group with formula
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
    • C07C15/20—Polycyclic condensed hydrocarbons
    • C07C15/27—Polycyclic condensed hydrocarbons containing three rings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
    • Y10S502/526—Sorbent for fluid storage, other than an alloy for hydrogen storage

Definitions

  • the present invention relates to a method for storing hydrogen capable of achieving the relatively light-weight and stable storage of hydrogen at or near the ordinary temperature and the ambient pressure and allowing easy takeoff of the stored hydrogen and also to a hydrogen clathrate which contains hydrogen and a production method thereof.
  • fuel cell is based on an energy conversion technology of taking electric energy out of hydrogen and oxygen by converting chemical energy, produced when hydrogen and oxygen react with each other to form water, into electric energy.
  • This technology draws attention as the most important next-generation technology to be used as a power source alternative to gasoline engine for vehicles, an on-site electric generator for household use, and a DC power supply for IT (information technology) use.
  • the method for storing hydrogen of the present invention is characterized in that organic compound is brought into contact with hydrogen gas in a pressurized state.
  • Organic compounds which can be used in the present invention do not include organic compounds consisting of carbon atoms only such as graphite, carbon nanotube, and fullerene and include organic metallic compounds containing metallic component.
  • the organic compound is basically solid, but may be liquid if it can enclose hydrogen in the pressurized state. In case of solid organic compound, it may be in crystalloid form or in amorphous form.
  • the molecular compound used in the present invention means a compound composed of two or more kinds of compounds each of which can stably exist alone in which such compounds are combined by relatively weak interaction, other than covalent bond, as typified by hydrogen bond and van der Waals force. Examples of such compounds include hydrate, solvate, addition compound, and clathrate.
  • the hydrogen molecular compound as mentioned above can be formed by bringing organic compound capable of forming a hydrogen molecular compound into contact with hydrogen under a pressurized condition so as to react.
  • the hydrogen molecular compound is relatively light weight and can store hydrogen at or near the ordinary temperature and the ambient pressure and allows emission of hydrogen therefrom by a simple method such as heating.
  • the hydrogen molecular compound according to the present invention may be a hydrogen clathrate in which hydrogen molecules are enclosed by contact reaction between organic compound and hydrogen molecules.
  • the hydrogen clathrate of the present invention is characterized in that hydrogen is enclosed by contact reaction between host compound and hydrogen.
  • the hydrogen By the contact reaction between host compound and hydrogen, the hydrogen can be selectively and stably enclosed in the host compound so that the hydrogen can be stored at the ordinary temperature and the ambient pressure and the stored hydrogen can be emitted at a relatively low temperature.
  • the host compound is preferably a host compound of multimolecular type, especially a phenol type host compound or an imidazole type host compound.
  • a production method of a hydrogen clathrate of the present invention is characterized by dissolving a host compound into a solvent, recrystallizing the host compound with injecting hydrogen into the solvent, and inserting hydrogen molecules into crystal lattice of the host compound. According to this method, the hydrogen clathrate in which hydrogen is enclosed into the host compound can be effectively produced at the ordinary temperature and the ambient pressure.
  • a production method of a hydrogen clathrate according to another embodiment of the present invention is characterized by bringing hydrogen gas into contact with a host compound in a pressurized state.
  • FIG. 1 is a graph showing the evaluation result of hydrogen storage performance of BHC in Example 1;
  • FIG. 2 is a graph showing the evaluation result of hydrogen storage performance of BHC in Example 2;
  • FIG. 3 is a graph showing the evaluation result of hydrogen storage performance of BA in Example 3.
  • FIG. 4 is a graph showing the evaluation result of hydrogen storage performance of THPEY in Example 4.
  • FIG. 5 is a graph showing the evaluation result of hydrogen storage performance of TMPE in Example 5.
  • FIG. 6 is a graph showing the evaluation result of hydrogen storage performance of TPE in Example 6;
  • FIG. 7 is a graph showing the evaluation result of hydrogen storage performance of DBDCA in Example 7.
  • FIG. 8 is a graph showing the evaluation result of hydrogen storage performance of FBDCA in Example 8.
  • FIG. 9 is a graph showing the evaluation result of hydrogen storage performance of TPBDM in Example 9.
  • FIG. 10 is a graph showing the evaluation result of hydrogen storage performance of TPHDD in Example 10.
  • FIG. 11 is a graph showing the evaluation result of hydrogen storage performance of CPPIZ in Example 11;
  • FIG. 12 is a graph showing the evaluation result of hydrogen storage performance of THPEA in Example 12;
  • FIG. 13 is a graph showing the evaluation result of hydrogen storage performance of HQ in Example 13;
  • FIG. 14 is a graph showing the evaluation result of hydrogen storage performance of urea in Example 14.
  • FIG. 15 is a graph showing the evaluation result of hydrogen storage performance of AC in Example 15;
  • FIG. 16 is a graph showing the evaluation result of hydrogen storage performance of CD in Example 16.
  • FIG. 17 is a graph showing the evaluation result of hydrogen storage performance of GAM in Example 17;
  • FIG. 19 is a graph showing the evaluation result of hydrogen storage performance of cellulose in Example 19;
  • FIG. 20 is a graph showing the evaluation result of hydrogen storage performance of chitosan in Example 20;
  • FIG. 21 is a graph showing the evaluation result of hydrogen storage performance of TTP in Example 21;
  • FIG. 22 is a graph showing IR spectrum of a hydrogen clathrate (Crystal A) produced in Example 22;
  • FIG. 23 is a graph showing IR spectrum of a methanol clathrate (Crystal B) produced in Example 22;
  • FIG. 24 is a graph showing the IR spectrum of FIG. 22 and IR spectrum of FIG. 23 superposed to each other;
  • FIG. 25 is a graph showing TG-DTA detection curve of hydrogen clathrate (Cristalline A) prepared in Example 22.
  • FIG. 26 is a graph showing TG-DTA detection curve of methanol clathrate (Cristalline B) prepared in Example 22.
  • an organic compound used in hydrogen storage may be any one of organic compounds capable of storing hydrogen when it is in contact with hydrogen gas under pressurized condition, except organic compounds consisting of carbon atoms only. Other than that, there is no particular limitation on the organic compound used in hydrogen storage.
  • the organic compound may contain metallic component and may not contain metallic component.
  • host compounds of monomolecular type include cyclodextrins, crown ethers, cryptands, cyclophanes, azacyclophanes, calixarenes, cyclotriveratrylenes, spherands, and cyclic oligopeptides.
  • host compounds of high-molecular type include celluloses, starchs, chitins, chitosans, and polyvinyl alcohols, polymers of polyethylene glycol arm type of which core is 1,1,2,2-tetrakis phenyl ethane, and polymers of polyethylene glycol arm type of which core is ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetrakis phenyl xylene.
  • host compounds of multimolecular type of which enclosure capacity is hardly influenced by the size of molecules of guest compound are preferable.
  • host compounds of multimolecular type are urea, 1,1,6,6-tetraphenyl-2,4-hexadiyn-1,6-diol, 1,1-bis(2,4-dimethylphenyl)-2-propyn-1-ol, 1,1,4,4-tetraphenyl-2-butyne-1,4-diol, 1,1,6,6-tetrakis(2,4-dimethylphenyl)-2,4-hexadiyn-1,6-diol, 9,10-diphyenyl-9,10-dihydroanthracene-9,10-diol, 9,10-bis(4-methylphenyl)-9,10-dihydroanthracene-9,10-diol, 1,1,2,2-tetraphenylethane-1,2-diol, 4-methoxyphenol, 2,4-dihydroxybenzophenone, 4,4,-dihydroxybenzophenone, 2,2′
  • These host compounds may be used alone or may be used in combination with one or more among the others.
  • the organic compound to be used is solid in powder form in view of contact efficiency with hydrogen gas.
  • the organic compound is not limited thereto and may be in granular form or in aggregated form and also may be in crystalloid form or in amorphous form. Further, the organic compound may be liquid or gaseous.
  • the organic compound is solid in powder form, there is no particular limitation on it particle diameter, but normally the particle diameter is preferably about 1 mm or less.
  • the organic compound may be used to be a complex material containing the organic compound supported on a porous carrier or support.
  • the porous carrier supporting the organic compound include, but not limited to, silicas, zeolites, or activated carbons, alternatively, interlaminar compounds such as a clay mineral or montmorillonite.
  • the complex material containing the organic compound can be manufactured by, for example, a method of dissolving the organic compound in a solvent capable of dissolving the organic compound, impregnating the porous carrier with the organic compound solution, drying the solvent, and decompressing and drying them.
  • the amount of the organic material supported on the porous carrier is normally in a range from 10 to 80% by weight relative to the porous carrier.
  • the aforementioned host compound such as 1,1-bis(4-hydroxyphenyl)cyclohexane or bis(dicyclohexylamide)diphenirate receives various guest molecules to form a crystal clathrate.
  • a clathrate is formed by bringing the host compound in contact with a guest compound (may be solid, liquid, or gaseous).
  • the gaseous molecular of hydrogen gas is brought in contact with the organic compound as the host compound in the pressurized state so that hydrogen molecules are enclosed in the clathrate, thereby stably storing hydrogen.
  • the pressurizing condition under which hydrogen gas and solid organic compound are in contact with each other, higher pressure is preferable because larger storage amount and higher storage speed of hydrogen are possible.
  • the pressurizer should be expensive and, in addition, it should be required to satisfy the regulations of High Pressure Gas Safety Law.
  • the pressurizing condition is higher than the 1.0 ⁇ 10 ⁇ 10 MPa and is preferably in a range from 1.0 ⁇ 10 ⁇ 10 MPa to 200 MPa. It is more preferably higher than the ambient pressure by 0.1 MPa to 70 MPa, actually especially by 0.1 to 0.9 MPa.
  • the contact time is longer, the hydrogen storage rate can be increased.
  • the contact time is preferably in a range from 0.01 to 24 hours.
  • the hydrogen gas to be brought in contact with the organic compound is preferably high-purity hydrogen. However, as will be described below, it may be a mixed gas of hydrogen gas and other gas in case of using host compound having selective enclosure capacity of hydrogen.
  • a hydrogen clathrate obtained as mentioned above is a hydrogen clathrate normally having hydrogen molecules from 0.1 to 20 moles relative to 1 mole of the host compound, but somewhat depends on the kind of used host compound and the contact condition with hydrogen.
  • Such a hydrogen clathrate as mentioned above can stably enclose hydrogen for a long period of time at ordinary temperature and ambient pressure. Moreover, the hydrogen clathrate is light as compared to hydrogen storage alloy and thus has excellent handling-property. In addition, since the hydrogen clathrate is solid, the hydrogen clathrate can be in powder form having particle diameter of 1 mm or less and thus can be easily stored and transported in a container made of glass, metal, or plastic.
  • the hydrogen in case that hydrogen is stored in the pressurized state, the hydrogen can be taken off from the stored state by depressurizing or heating.
  • the hydrogen can be taken off from the stored state also by heating and depressurizing at the same time.
  • JIS Japan Industrial Standard
  • H-7201 entitled “Method of termining the PCT relations of hydrogen absorbing alloys”
  • the measurement was conducted by using a hydrogen emission evaluation equipment available from LESCA CORPORATION.
  • test tube having volume of 25 ml was filled with specimen of about 0.1 g to 1 g, and the weight of the specimen was measured precisely.
  • the test tube was then filled with helium gas, and was measured its airtightness for more than 12 hours. It was found to have enough airtightness. After that, the inner volume of the tube other than the specimen was detected.
  • the specimen was heated to 50° C. and was vacuumed and depressurized for 3 hours by a rotary pump.
  • the test tube filled with the specimen was retained in a temperature-controlled bath at 25° C. during the test. Hydrogen gas was introduced with changing the pressure to balance the pressure. When the pressure was balanced, the storage amount was measured. The measurement was conducted under such a condition that the retention time at each balanced pressure was 1 hour or 8 hours.
  • BHC 1,1-bis(4-hydroxyphenyl)cyclohexane
  • Example 2 0.2361 g of the BHC in solid power state, used in Example 1, of which hydrogen was emitted was prepared as a specimen.
  • the specimen was evaluated according to the aforementioned test method under such a condition that the retention time at each pressure was 8 hour.
  • the relation between the balanced pressure and the hydrogen storage rate was shown in Table 2 and FIG. 2 .
  • BA 9,9′-bianthryl
  • THPEY 1,1,2,2-tetrakis (4-hydroxyphenyl) ethylene
  • TMPE tetrakis(p-methoxyphenyl)ethylene
  • TPE 1,1,2,2-tetraphenylethane
  • DBDCA bis-dicyclohexylamide diphenirate
  • FBDCA bis-dicyclohexylamide fumarate
  • TPBDM ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetraphenyl-1,1′-biphenyl-2,2′-dimethanol
  • TPHDD 1,1,6,6-tetraphenyl-2,4-hexadiyn-1,6-diol
  • CPPZZ 2-(m-cyanophenyl)phenanthro[9,10-d]imidazole
  • TPEA 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane
  • AC acetylene dicarboxyl acid
  • CD ⁇ -cyclodextrin
  • GAM methyl gallate
  • DCA deocycholic acid
  • TTP tri-m-tolylphosphine
  • hydrogen can be stored at the ordinary temperature and the ambient pressure, thereby eliminating the necessity of a pressure tight vessel, a cryogenic vessel, and the like. Therefore, the storage and transport of hydrogen in relatively compact and light form is be achieved and, in addition, stored hydrogen can be easily emitted and used for various applications.
  • host compound so that the host compound for enclosing hydrogen is any of compounds capable of enclosing hydrogen.
  • Known host compounds are organic compounds of monomolecular type, multimolecular type, high-molecular type, and the like as described with regard to the method of hydrogen storage of the present invention and inorganic host compounds.
  • the inorganic host compounds include clay minerals, montmorillonites, and zeolites.
  • host compounds of multimolecular type of which enclosure capacity is hardly influenced by the size of molecules of guest compound are preferable.
  • phenol-based host compounds such as 1,1-bis(4-hydroxyphenyl)cyclohexane are advantageous in view of enclosure capacity and industrial ready availability.
  • the solvent for dissolving the host compound may be any of solvents capable of dissolving the host compound and is suitably selected according to the kind of the host compound.
  • any of solvents including alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, ethers such as diethyl ether and dibutyl ether, furans such as etrahydrofuran, amides such as dimethyl acetamide, and aldehydes such as acetaldehyde and benzaldehyde can be employed as a solvent for a host compound of multimolecular type such as a phenol-based host compound as mentioned above.
  • concentration of the host compound in the solvent there is no particular limitation on the concentration of the host compound in the solvent because the solubility depends on the kind of host compound and the kind of solvent.
  • the hydrogen clathrate obtained in the aforementioned manner is a hydrogen clathrate normally having hydrogen molecules from 0.2 to 20 moles relative to 1 mole of the host compound, but somewhat depends on the kind of used host compound and the contact condition with hydrogen.
  • the hydrogen clathrate thus obtained can stably enclose hydrogen for a long period of time at the ordinary temperature and the ambient pressure. Moreover, the hydrogen clathrate is light as compared to hydrogen storage alloy and thus has excellent handling property. In addition, the hydrogen clathrate can be easily stored and transported in a container made of glass, metal, or plastic.
  • the hydrogen can be taken off from the hydrogen clathrate by heating the hydrogen clathrate to a temperature in a range from 30° C. to 200° C., particularly in a range from 40° C. to 100° C.
  • the temperature somewhat depends on the kind of host compound. Accordingly, hydrogen can be easily emitted from the hydrogen clathrate and collected.
  • Hydrogen clathrate produced by injecting hydrogen into a solvent containing dissolved host compound as mentioned above normally consists of two components of the host compound and the hydrogen.
  • the hydrogen clathrate includes used solvent in addition to host compound and hydrogen, that is, consist of three components of the host compound, the hydrogen, and the solvent.
  • the hydrogen clathrate has a difference of 20° C. through 30° C. between the emission temperature of solvent and the emission temperature of hydrogen. In this case, it is especially preferable that the used solvent having a boiling point higher than the emission temperature of the hydrogen.
  • BHC 1,1-bis(4-hydroxyphenyl)cyclohexane
  • 3 ml of methanol were put in a sample bottle and mixed so that the BHC was dissolved.
  • hydrogen was bubbled from a commercially available gas cylinder into the solvent, the methanol as solvent evaporates, thereby obtaining crystals.
  • crystals were air-dried for 1 hour under room temperature to vaporize the methanol (Crystal A).
  • Crystal B a solvent obtained by dissolving 0. 2 g of BHC in 3 ml of methanol was left without reaction (with hydrogen). Crystals thus deposited were taken (Crystal B).
  • the IR spectrum measurements were made on Crystals A and B obtained above. The results of the measurements are shown in FIGS. 20 and 21 , respectively, and the superposed data of these results is shown in FIG. 22 . From FIGS. 20 through 23 showing IR spectrums, the IR spectrums of the crystal A and Crystal B are clearly different from each other in a range from 3100 to 3700 cm ⁇ 1 and around 1200 cm ⁇ 1 depending on the hydrogen group of BHC as the host compound. This makes sure that different crystals were obtained.
  • Crystal B has a component (it may be methanol) which evaporates in a temperature range of 80° C. to 110° C. and Crystal A has components which evaporate in two stages of a temperature range less than 50° C. and a temperature range around 80° C. This means that Crystal A has a component which evaporates in a temperature range less than 50° C. and which was not found in Crystal B.
  • the hydrogen clathrate and the production method thereof of the present invention can exhibit the following excellent effects:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US10/804,108 2002-06-19 2004-03-19 Method for storing hydrogen, hydrogen clathrate compound and production method thereof Expired - Lifetime US7220294B2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2002-178755 2002-06-19
JP2002178755 2002-06-19
JP2003-024590 2003-01-31
JP2003024590 2003-01-31
PCT/JP2003/007318 WO2004000857A1 (ja) 2002-06-19 2003-06-10 水素貯蔵方法、水素包接化合物及びその製造方法

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2003/007318 Continuation WO2004000857A1 (ja) 2002-06-19 2003-06-10 水素貯蔵方法、水素包接化合物及びその製造方法

Publications (2)

Publication Number Publication Date
US20040230084A1 US20040230084A1 (en) 2004-11-18
US7220294B2 true US7220294B2 (en) 2007-05-22

Family

ID=30002237

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/804,108 Expired - Lifetime US7220294B2 (en) 2002-06-19 2004-03-19 Method for storing hydrogen, hydrogen clathrate compound and production method thereof

Country Status (10)

Country Link
US (1) US7220294B2 (ja)
EP (1) EP1428831A4 (ja)
JP (2) JP4617880B2 (ja)
KR (1) KR100653662B1 (ja)
CN (1) CN100519570C (ja)
AU (1) AU2003242146A1 (ja)
CA (1) CA2482087C (ja)
MY (1) MY133622A (ja)
TW (1) TW200400935A (ja)
WO (1) WO2004000857A1 (ja)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899006B (zh) 2002-08-19 2013-11-06 劳洛斯治疗公司 2，4，5-三取代的咪唑及其作为抗菌剂的用途
JP2004142985A (ja) * 2002-10-23 2004-05-20 Kurita Water Ind Ltd 水素放出装置
DK1692113T3 (en) * 2003-11-14 2018-01-08 Lorus Therapeutics Inc ARYLIMIDAZOLES AND USE THEREOF AS ANTICANCES
EP1705740A4 (en) 2003-12-18 2009-02-25 Kurita Water Ind Ltd FUEL FOR FUEL CELL, FUEL CELL AND USE THEREOF
JP4631309B2 (ja) * 2004-05-14 2011-02-16 栗田工業株式会社 固体電解質型燃料電池用燃料、固体電解質型燃料電池及びその使用方法
NL1025907C2 (nl) * 2004-04-08 2005-10-11 Univ Delft Tech Waterstofopslag.
JP2006079838A (ja) * 2004-09-07 2006-03-23 Konica Minolta Holdings Inc 燃料電池用燃料およびこれを用いた燃料電池
JP2006095389A (ja) * 2004-09-28 2006-04-13 Kurita Water Ind Ltd 水素水の製造方法および電子部品の洗浄方法
JP4792725B2 (ja) * 2004-09-29 2011-10-12 栗田工業株式会社 水素貯蔵方法
JP5062421B2 (ja) * 2005-05-13 2012-10-31 栗田工業株式会社 水素貯蔵方法
CA2611032C (en) 2005-05-25 2012-01-17 Genesense Technologies Inc. 2-indolyl imidazo[4,5-d]phenanthroline derivatives and their use in the treatment of cancer
US7901661B2 (en) * 2005-12-21 2011-03-08 The Penn State Research Foundation Synthesis of hydrogen-carbon clathrate material and hydrogen evolution therefrom at moderate temperatures and pressures
US7749304B2 (en) * 2006-01-30 2010-07-06 General Electric Company Method for storing hydrogen, and related articles and systems
US7553996B2 (en) * 2007-03-06 2009-06-30 Conant Lawrence D Gas clathrate hydrate compositions, synthesis and use
CN101804963B (zh) * 2010-03-31 2012-05-09 华南理工大学 一种氢笼型化合物复合储氢的方法
CN101798060B (zh) * 2010-03-31 2012-05-23 华南理工大学 一种以笼型结构复合储氢方法
US9309247B2 (en) 2013-03-20 2016-04-12 Lorus Therapeutics Inc. 2-substituted imidazo[4,5-D]phenanthroline derivatives and their use in the treatment of cancer
WO2015051304A1 (en) 2013-10-04 2015-04-09 Aptose Biosciences Inc. Compositions, biomarkers and their use in treatment of cancer
CN104761485A (zh) * 2015-03-09 2015-07-08 中国科学院成都生物研究所 一种新型的储氢材料及氢的解析方法
KR102112786B1 (ko) * 2015-08-19 2020-05-20 롬엔드하스전자재료코리아유한회사 유기 전계 발광 화합물 및 이를 포함하는 유기 전계 발광 소자
KR20170051198A (ko) 2015-10-30 2017-05-11 롬엔드하스전자재료코리아유한회사 전자 버퍼 재료, 전자 전달 재료, 및 이를 포함하는 유기 전계 발광 소자
BR112020001201B1 (pt) * 2017-07-19 2023-03-21 Beijing Research Institute Of Chemical Industry, China Petroleum & Chemical Corporation Sistema catalisador ziegler-natta para polimerização olefínica, componente catalisador sólido para polimerização olefínica e processo de polimerização olefínica
CN111417395A (zh) 2017-10-30 2020-07-14 艾普托斯生物科学公司 用于治疗癌症的芳基咪唑
CN108006431A (zh) * 2017-12-09 2018-05-08 芜湖瑞德机械科技有限公司 具有优异使用寿命的绝热气瓶
CN109252984A (zh) * 2018-09-06 2019-01-22 北京铂陆氢能科技开发有限公司 一种基于有机液体储氢材料的储能和分布式电源发电系统
KR102107929B1 (ko) * 2019-01-31 2020-05-07 한국해양대학교 산학협력단 하이드로퀴논-레조시놀 복합 포접화합물 및 이를 이용한 저분자 가스 포획 또는 저장 방법
JP7372130B2 (ja) * 2019-12-09 2023-10-31 日東電工株式会社 水素貯蔵方法、水素ガスの製造方法及び水素ガス製造システム
CN111204706B (zh) * 2020-01-15 2023-05-23 华南理工大学 一种利用h型水合物储氢的方法
FR3135629A1 (fr) * 2022-05-20 2023-11-24 Université De Pau Et Des Pays De L'adour Composite poreux et son utilisation pour le stockage de gaz

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5187191A (ja) 1975-01-29 1976-07-30 Kogyo Gijutsuin
JPS5314513A (en) 1976-07-26 1978-02-09 Hitachi Ltd Interface conversion device
US5082654A (en) 1988-10-28 1992-01-21 Kurita Water Industries Ltd. Clathrate compound and process for stabilizing diethyltoluamide
US5091400A (en) * 1988-12-28 1992-02-25 Kurita Water Industries Ltd. Clathrate compound
US5523020A (en) * 1993-10-01 1996-06-04 Kurita Water Industries Ltd. Clathrate compound including water-soluble microbicide
US5703378A (en) 1995-04-18 1997-12-30 Sandia Corporation Materials for the scavanging of hydrogen at high temperatures
JP2000210559A (ja) 1999-01-22 2000-08-02 Osaka Gas Co Ltd ガス貯蔵性有機金属錯体、その製造方法およびガス貯蔵装置
US6290753B1 (en) * 1998-02-06 2001-09-18 Institutt For Energiteknikk Hydrogen storage in carbon material
JP2001261301A (ja) 2000-03-16 2001-09-26 Toyota Central Res & Dev Lab Inc 有機物系水素貯蔵材料および水素貯蔵方法
US6309449B1 (en) * 1997-10-10 2001-10-30 Mannesmann Ag Gas accumulator
JP2001300305A (ja) 2000-04-21 2001-10-30 Toyota Motor Corp 水素吸蔵材料
US20020020292A1 (en) * 2000-07-07 2002-02-21 Wojtowicz Marek A. Microporous carbons for gas storage
JP2002106791A (ja) 2000-09-29 2002-04-10 Honda Motor Co Ltd ボイルオフガス処理装置
WO2002048074A1 (fr) 2000-12-11 2002-06-20 Nippon Soda Co.,Ltd. Procede de preparation d'un compose moleculaire
JP2002275673A (ja) 2001-03-16 2002-09-25 Norio Kudo 電力貯蔵装置
US20030089117A1 (en) * 2001-10-30 2003-05-15 Carnegie Institute Of Washington Composition and method for hydrogen storage
US6634321B2 (en) * 2000-12-14 2003-10-21 Quantum Fuel Systems Technologies Worldwide, Inc. Systems and method for storing hydrogen

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2457709A1 (fr) * 1979-05-29 1980-12-26 Anvar Nouveaux agents d'adsorption de gaz utiles en particulier pour separer de l'hydrogene d'une phase le renfermant
JPS56139129A (en) * 1980-04-02 1981-10-30 Toyo Soda Mfg Co Ltd Zeolite occluding agent
JP2508651B2 (ja) * 1986-07-30 1996-06-19 栗田工業株式会社 包接化合物の製造方法
JPH0240304A (ja) * 1988-07-27 1990-02-09 Kanebo Ltd 徐放性抗菌剤
JPH06115901A (ja) * 1992-10-01 1994-04-26 Jena Purusotam 新規な水素貯蔵物質、装置及びその利用
JP3839859B2 (ja) * 1994-12-28 2006-11-01 日本曹達株式会社 包接化合物の製造方法
JP2001056099A (ja) * 1999-08-18 2001-02-27 Toyota Motor Corp 水素貯蔵方法
JP2003212800A (ja) * 2002-01-23 2003-07-30 Nippon Oil Corp ナフタレンの水素化によるデカリンの製造方法
JP2004083385A (ja) * 2002-06-04 2004-03-18 Sekisui Chem Co Ltd 水素供給媒体およびそれを利用した水素貯蔵・供給システム
JP2004026759A (ja) * 2002-06-27 2004-01-29 Sekisui Chem Co Ltd 水素供給体の製造方法

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5187191A (ja) 1975-01-29 1976-07-30 Kogyo Gijutsuin
JPS5314513A (en) 1976-07-26 1978-02-09 Hitachi Ltd Interface conversion device
US5082654A (en) 1988-10-28 1992-01-21 Kurita Water Industries Ltd. Clathrate compound and process for stabilizing diethyltoluamide
US5091400A (en) * 1988-12-28 1992-02-25 Kurita Water Industries Ltd. Clathrate compound
US5523020A (en) * 1993-10-01 1996-06-04 Kurita Water Industries Ltd. Clathrate compound including water-soluble microbicide
US5703378A (en) 1995-04-18 1997-12-30 Sandia Corporation Materials for the scavanging of hydrogen at high temperatures
US6309449B1 (en) * 1997-10-10 2001-10-30 Mannesmann Ag Gas accumulator
US6290753B1 (en) * 1998-02-06 2001-09-18 Institutt For Energiteknikk Hydrogen storage in carbon material
JP2000210559A (ja) 1999-01-22 2000-08-02 Osaka Gas Co Ltd ガス貯蔵性有機金属錯体、その製造方法およびガス貯蔵装置
JP2001261301A (ja) 2000-03-16 2001-09-26 Toyota Central Res & Dev Lab Inc 有機物系水素貯蔵材料および水素貯蔵方法
JP2001300305A (ja) 2000-04-21 2001-10-30 Toyota Motor Corp 水素吸蔵材料
US20020020292A1 (en) * 2000-07-07 2002-02-21 Wojtowicz Marek A. Microporous carbons for gas storage
JP2002106791A (ja) 2000-09-29 2002-04-10 Honda Motor Co Ltd ボイルオフガス処理装置
WO2002048074A1 (fr) 2000-12-11 2002-06-20 Nippon Soda Co.,Ltd. Procede de preparation d'un compose moleculaire
US6634321B2 (en) * 2000-12-14 2003-10-21 Quantum Fuel Systems Technologies Worldwide, Inc. Systems and method for storing hydrogen
JP2002275673A (ja) 2001-03-16 2002-09-25 Norio Kudo 電力貯蔵装置
US20030089117A1 (en) * 2001-10-30 2003-05-15 Carnegie Institute Of Washington Composition and method for hydrogen storage

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI, Section ch, Week 199012, Derwent Publications Ltd., London, GB; AN1990-087253, XP 002394367, JP02 040304, Feb. 9, 1990.
DATABASE WPI, Section ch, Week 199638, Derwent Publications Ltd., London, GB; An1996-379259, XP-002394368, JP08 183744, Jul. 16, 1996.
International Journal of Hydrogen Energy, L.M.Das, vol. 21, P789800, On-boad hydrogen storage systems for automotive application (1996.9).
Patent Abstract of Japan, vol. 012, No. 248 (C-511), Jul. 13, 1988, JP 63 035533.
Vos W L et al; "Novel H2-H2O clathrates at high pressures" Physical Revie Letters, American Physical Society, New York, US, vol. 71, No. 19, Nov. 8, 1993, pp. 3150-3153, XP002231837.

Also Published As

Publication number Publication date
JP4617880B2 (ja) 2011-01-26
JP2009203159A (ja) 2009-09-10
EP1428831A1 (en) 2004-06-16
CA2482087C (en) 2011-04-19
TW200400935A (en) 2004-01-16
TWI294418B (ja) 2008-03-11
US20040230084A1 (en) 2004-11-18
KR20050013192A (ko) 2005-02-03
CN100519570C (zh) 2009-07-29
MY133622A (en) 2007-11-30
CA2482087A1 (en) 2003-12-31
AU2003242146A1 (en) 2004-01-06
EP1428831A4 (en) 2006-09-20
JPWO2004000857A1 (ja) 2005-10-20
WO2004000857A1 (ja) 2003-12-31
KR100653662B1 (ko) 2006-12-05
CN1659174A (zh) 2005-08-24

Similar Documents

Publication Publication Date Title
US7220294B2 (en) Method for storing hydrogen, hydrogen clathrate compound and production method thereof
Yang et al. POM‐incorporated CoO nanowires for enhanced photocatalytic syngas production from CO2
Pinkerton et al. Thermogravimetric measurement of hydrogen absorption in alkali-modified carbon materials
Ding et al. A Heterogeneous Metal‐Free Catalyst for Hydrogenation: Lewis Acid–Base Pairs Integrated into a Carbon Lattice
Yang et al. A Core–Shell‐Structured Silver Nanowire/Nitrogen‐Doped Carbon Catalyst for Enhanced and Multifunctional Electrofixation of CO2
Minkina et al. Stability of alkaline aqueous solutions of sodium borohydride
Li et al. Ultrasonic chemical oxidative degradations of 1, 3-dialkylimidazolium ionic liquids and their mechanistic elucidations
Hassan et al. Effects of Graphene Oxide Nanosheets and Al2O3 Nanoparticles on CO2 Uptake in Semi‐clathrate Hydrates
Shao et al. Scalable Electrosynthesis of formamide through C− N coupling at the industrially relevant current density of 120 mA cm− 2
Zhu et al. Crystallohydrate loaded halloysite nanocontainers for thermal energy storage
Xu et al. Selective CO2 Electroreduction to Formate on Polypyrrole‐Modified Oxygen Vacancy‐Rich Bi2O3 Nanosheet Precatalysts by Local Microenvironment Modulation
Liu et al. MoS2 nano‐flowers stacked by ultrathin sheets coupling with oxygen self‐doped porous biochar for efficient photocatalytic N2 fixation
Yi et al. N‐Doped Carbon Aerogel Derived from a Metal–Organic Framework Foam as an Efficient Electrocatalyst for Oxygen Reduction
CN102887498A (zh) 掺氮石墨烯的制备方法
Cheng et al. Photocatalytic selective oxidation of HMF to DFF over Bi2WO6/mpg–C3N4 composite under visible light
Okunaka et al. Z‐Scheme Water Splitting under Near‐Ambient Pressure using a Zirconium Oxide Coating on Printable Photocatalyst Sheets
JP2005203335A (ja) 燃料電池用燃料及びその供給方法
Lazzarini et al. Boronation of biomass-derived materials for hydrogen storage
JP4848614B2 (ja) 水素貯蔵方法
JP2007320799A (ja) 水素吸蔵炭素
Carini et al. Wall‐and Hybridisation‐Selective Synthesis of Nitrogen‐Doped Double‐Walled Carbon Nanotubes
JP2006096609A (ja) 水素貯蔵方法
Bartoli et al. Unraveling the Effect of Carbon Nanotube Oxidation on Solid-State Decomposition of Ammonia Borane/Carbon Nanotube Composites
JP2004259480A (ja) 燃料電池発電システム
Oshima et al. Preparation of Solid‐Solution TiS2− xSex Nanosheets by Liquid Phase Exfoliation

Legal Events

Date Code Title Description
AS Assignment

Owner name: KURITA WATER INDUSTRIES LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:YAGI, MINORU;REEL/FRAME:015351/0437

Effective date: 20040316

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553)

Year of fee payment: 12